Rolled or extruded aluminium al-mn alloy products with improved corrosion resistance

ABSTRACT

The tamperproof closing device for a receptacle having a threaded collar comprises a screw cap ( 1 ) consisting of a bottom ( 8 ) and a cylindrical skirt ( 9 ) having inner threading for co-operation with the corresponding threading ( 5 ) on the collar ( 2 ) and extended by a tamperproof ring ( 13 ) which is attached by frangible means ( 20 ). The collar has a plurality of outer radial notches arranged at the base thereof. Said notches are circumferentially oriented and the ring comprises a plurality of inner radial reliefs ( 15 ) whose profile is complementary to that of the notches ( 7 ). The orientations and dimensions of the notches ( 7 ) and reliefs ( 15 ) are determined in such a way that the second items can pass onto the first items in the direction of screwing as a result of elastic deformation of the constitutive material and can prevent the same from occurring in the opposite direction. The reliefs ( 15 ) are formed on an annular lip ( 14 ) which is turned back and originates from the tamperproof ring ( 13 ). When it leaves the mould, said lip ( 14 ) forms an annular truncated appendix converging slightly towards the inside and bearing the reliefs on the outside ( 15 ).

FIELD OF THE INVENTION

[0001] The invention relates to rolled or extruded aluminium Al—Mn alloy products (series 3000 according to the Aluminium Association nomenclature) with improved corrosion resistance, and particularly to tubes intended largely for pipes or tubes and strips for use in heat exchangers for motor vehicles.

STATE OF THE ART

[0002] The most frequently used alloys for tubes to be used as pipes for motor vehicles, and for tubes and strips for use in mechanically assembled automobile heat exchangers are manganese 3102, 3003 and 3103 alloys according to standard EN 573-3. These alloys are suitable for extrusion and have satisfactory mechanical properties. However, it became necessary to improve the corrosion resistance of these applications, which lead to the development of “long life” alloys.

[0003] Patent application WO 97/46726 by Reynolds Metals applies to an alloy known as X3030 with composition (% by weight):

[0004] Mn 0.1-0.5; Cu<0.03; Mg<0.01; Zn 0.06-1.0; Si 0.05-0.12; Fe<0.50; Ti 0.03-0.30; Cr<0.50, the balance consisting of aluminium. The addition of Zn and Ti contributes to improving the corrosion resistance. Cr is preferably held below 0.20% and the examples have contents of 0.005%, 0.05% and 0.10%. Fe is preferably kept below 0.30% and the examples have contents of 0.10%, 0.12% and 0.20%.

[0005] Patent application WO 99/18250 by the same company applies to an alloy known as X3020 with better formability than X3030 by the addition of Mg (up to 1%) and Zr (up to 0.30%). Cr is preferably kept below 0.02%, or even 0.01%. Fe is preferably kept below 0.30%.

[0006] Patent application WO 00/50656 by Norsk Hydro relates to an alloy with composition Si 0.05-0.15; Fe 0.06-0.35; Cu<0.10; Mn 0.01-1.0; Mg 0.02-0.60; Cr<0.25; Zn 0.05-0.70; Ti<0.25; Zr<0.20.

[0007] Cr is preferably kept below 0.15% and is only allowed to enable recycling of manufacturing waste from other alloys. Fe is preferably kept below 0.22%.

PURPOSE OF THE INVENTION

[0008] The purpose of the invention is to further improve the corrosion resistance compared with existing “long life” alloys.

[0009] The invention concerns a rolled or extruded product, in particular a tube, made of an alloy composition (expressed in wt. %) comprising:

[0010] Si<0.30; Fe 0.20-0.50; Cu<0.05; Mn 0.5-1.2; Mg<0.05; Zn<0.50; Cr 0.10-0.30; Ti<0.05 Zr<0.05; the balance consisting of aluminium and unavoidable impurities.

[0011] The preferred contents are Si<0.15; Fe 0.25-0.40; Mn 0.8-1.0; Cr 0.15-0.30; Zn 0.10-0.25.

[0012] The invention also concerns a method for making tubes extruded of said composition comprising casting a billet with the above composition, optionally homogenizing it, extruding a tube, drawing said tube in one or several passes and continuous annealing at a temperature ranging between 350 and 500° C. with a temperature increase of less than 10 seconds and preferably less than 2 seconds.

[0013] The invention also concerns a method for making strips with this composition, comprising casting a plate, hot rolling and then cold rolling it, and continuous annealing at a temperature ranging between 350 and 500° C. with a temperature increase of less than 10 minutes, and preferably less than 2 minutes.

DESCRIPTION OF THE INVENTION

[0014] The alloy according to the invention has a manganese content of the same order of magnitude as the 3003 and 3103 alloys and contains almost no copper or magnesium. Unlike what is believed in prior art which recommends low iron contents for corrosion resistance, the behaviour of the alloy is good with an iron content of more than 0.20% and up to 0.50%. This avoids the need to use a more expensive pure aluminium base. Also unlike prior art, a chromium content of more than 0.10% and preferably 0.15% is shown to be favourable to corrosion resistance. Addition of a low content of zinc, less than 0.50% and preferably less than 0.20%, is also favourable.

[0015] The method for making extruded product, comprises casting the billets of the indicated alloy, homogenizing the billets, heating and extruding them to obtain a straight or ring tube, and one or several drawing passes to bring the product to the required dimensions. The tube is then annealed by taking it through a passage furnace, preferably an induction furnace, at high speed. The extruded product is heated very quickly, in less than 10 seconds and preferably in less than 2 seconds, and the product advances at a speed of between 20 and 200 m/mn. The furnace temperature is kept between 350 and 500° C. The product can then be drawn again to increase the mechanical strength.

[0016] This continuous annealing gives a microstructure with fine equiaxial grains, a medium grain size as measured by the intercepts method of less than 40 μm and typically of the order of 30 μm, while with conventional annealing in a static furnace, the grains are elongated with a much larger grain size of the order of 180 μm in the extrusion direction and 70 μm in the direction perpendicular to extrusion. The presence of chromium tends to further reduce the grain size by increasing the density of the recrystallisation sites, which has a beneficial effect on corrosion resistance.

[0017] The method for making strips comprises casting a plate with a composition according to the invention, optionally homogenizing this plate, hot rolling this plate to obtain a strip, cold rolling this strip to the required thickness and final recrystallisation annealing to a temperature ranging between 350 and 600° C. This final annealing is preferably done continuously in a passage furnace with a temperature increase in less than 10 minutes and preferably less than 2 minutes, which gives a fine grain size. The hot rolled strip may also be obtained directly by continuous casting, for example by casting between two cooled cylinders.

[0018] The products according to the invention have better corrosion resistance than the 3003 and 3103, and at least as good as “long life” alloys according to prior art, mechanical properties and formability equivalent to 3003 or 3103, and an economical production cost. They have an electromechanical corrosion potential practically identical to that of 3003 or 3103, such that there is no difference in behaviour of galvanic couples, for example the tube-fin couple in heat exchangers. The extrudability of extruded products is also at least as good as the extrudability of 3003 or 3103 alloys.

[0019] Extruded products according to the invention can be used particularly as fuel, oil or brake fluid pipes for automobiles and as tubes for heat exchangers in engine cooling systems and air conditioning systems for passenger compartments in motor vehicles. The strips may be used in the same heat exchangers for header pipes, evaporators and fins.

EXAMPLE

[0020] Billets made of 6 alloys identified A to F were cast and homogenized. The compositions of alloys A, B and C were the same as the compositions of 3003, 3103 and X3020 according to prior art. Alloys D and E are different from the invention in that D has a lower iron content and E contains titanium instead of chromium. The alloy F is conform with the invention. The compositions of the alloys (% by weight) are shown in table 1. TABLE 1 Ref. Si Fe Cu Mn Mg Cr Zn Ti A 0.09 0.19 0.15 1.05 — — — — B 0.12 0.55 — 1.10 — — — — C 0.07 0.08 — 0.95 — — 0.17 0.14 D 0.08 0.10 — 1.00 — 0.20 0.01 0.02 E 0.07 0.26 — 0.98 — 0.01 0.01 0.14 F 0.08 0.27 — 0.98 — 0.19 0.17 0.01

[0021] The billets were extruded in coiled tubes and were then drawn to obtain a diameter of 12 mm and a thickness of 1.25 mm. No significant difference in terms of extrudability or drawing was found for any of the six alloys. These coiled tubes were continuously annealed in an induction furnace at a fixed temperature of 470° C. with an advance speed of between 60 and 120 m/min. The rings were then drawn once again to bring them into the H12 state according to standard EN 515. The ultimate strength R_(m) (in MPa) and the yield stress R_(0.2) (in MPa) were then measured on the samples of the 6 tubes. The results are given in table 2. TABLE 2 Alloy A B C D E F R_(m) 116 120 106 112 112 116 R_(0.2) 102 113 95 106 98 108

[0022] It can be seen that the mechanical strength of the alloy according to the invention is almost exactly the same as the alloy according to 3003 (A) or 3103 (B).

[0023] The corrosion resistance was measured using the SWAAT (salt water acetic acid test) test according to standard ASTM G85. Measurements were made for three different cycle times, 100, 400 and 800 cycles on two 200 mm tubes per alloy and per duration. At the end of the test, the tubes were taken out of the containment and were pickled using a 68% concentrated nitric acid solution to dissolve corrosion products. The depth of the 5 deepest pits formed was then measured on each tube, and the average for each tube and the average P_(moy) of the values obtained for the two tubes were calculated. The corrosion resistance is better when P_(moy) is smaller. The results are given in table 3. TABLE 3 Alloy A B C D E F 100 cycles 273 220 101 91 164 91 400 cycles 462 375 213 134 151 124 800 cycles 1054 431 368 260 387 249

[0024] It can be seen that alloy F according to the invention is the alloy that gives the best results, and therefore the iron content of 0.27% does not reduce the corrosion resistance, and the addition of 0.20% of chromium for alloys D and F has a significantly beneficial effect. 

1. A rolled or extruded product, in particular a tube, made of an alloy composition (expressed in wt. %) comprising: Si<0.30; Fe 0.20-0.50; Cu<0.05; Mn 0.5-1.2; Mg<0.05; Zn<0.50; Cr 0.10-0.30; Ti<0.05 Zr<0.05; the balance consisting of aluminium and unavoidable impurities.
 2. Product according to claim 1, characterized in that Si<0.20.
 3. Product according to either claim 1 or 2, characterized in that the Fe content is between 0.25 and 0.40.
 4. Product according to one of claims 1 to 3, characterized in that the Mn content is between 0.8 and 1.0.
 5. Product according to one of claims 1 to 4, characterized in that the Cr content is between 0.15 and 0.30.
 6. Product according to one of claims 1 to 5, characterized in that the Zn content is between 0.10 and 0.25.
 7. Extruded product according to one of claims 1 to 6, characterized in that its grain size is less than 40 μm.
 8. Method for making extruded tubes according to one of claims 1 to 7, comprising casting a billet, optionally homogenizing it, extruding a tube, drawing said tube in one or several passes and continuous annealing at a temperature ranging between 350 and 500° C. with a temperature increase of less than 10 seconds.
 9. Method according to claim 8, characterized in that the temperature increases in less than 2 seconds.
 10. Method according to either claim 8 or 9, characterized in that annealing is made in an induction furnace.
 11. Method according to one of claims 8 to 10, characterized in that annealing is followed by drawing.
 12. Use of an extruded product according to one of claims 1 to 7, for tubes to be used as pipes for motor vehicles.
 13. Use of an extruded product according to one of claims 1 to 7, for tubes for use in automobile heat exchangers.
 14. Method for making strips according to one of claims 1 to 7, comprising casting a plate, optionally homogenizing this plate, hot rolling this plate to obtain a strip, cold rolling this strip to the required thickness and final recrystallisation annealing at a temperature ranging between 350 and 600° C. with a temperature increase of less than 10 minutes, and preferably less than 2 minutes.
 15. Use of a strip according to one of claims 1 to 7, as an element for an automobile heat exchanger. 